Activation of Chiral (Salen)TiCl<sub>2</sub> Complex by Phosphorane for the Highly Enantioselective Cyanation of Nitroolefins
Chen Chen, Wen‐Biao Wu, Yanhong Li, Qiuhua Zhao, Jin‐Sheng Yu, Jian Zhou
Abstract
We report that phosphorane can activate (salen)TiCl2 complex to achieve unprecedented excellent enantioselectivity and a broad substrate scope in the cyanation of nitroolefins. Our cyanating reagent Me2(CH2Cl)SiCN proves to be more active than TMSCN in this reaction, allowing 11 β-aliphatic nitrolefins and 12 β-CF3 nitroolefins (either β-aryl or aliphatic) to work well to give the corresponding tertiary or quaternary β-nitronitriles with high to excellent enantioselectivity.
Topics & Concepts
PhosphoraneChemistryCyanationEnantioselective synthesisReagentSubstrate (aquarium)ArylCombinatorial chemistryMedicinal chemistryOrganic chemistryStereochemistryCatalysisGeologyAlkylOceanographyChemical Synthesis and AnalysisAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and Catalysis